利用多功能、多用途的可再生甲酸实现化学品的绿色与可持续合成（英文）  

Formic acid: A versatile renewable reagent for green and sustainable chemical synthesis

作　　者：柳翔[1] 李舒爽 刘永梅[1] 曹勇[1] 

机构地区：[1]复旦大学化学系,上海市分子催化和功能材料重点实验室,上海200433

出　　处：《催化学报》2015年第9期1461-1475,共15页

基　　金：supported by the National Natural Science Foundation of China(21273044,21473035);the Research Fund for the Doctoral Program of Higher Education(20120071110011);Science & Technology Commission of Shanghai Municipality(08DZ2270500,12ZR1401500)~~

摘　　要：近年来,随着化石资源日趋短缺以及由此带来的人类生存环境日益恶化,生物质等可再生资源的高效、可持续利用已成为各国科学家研究与关注的焦点.甲酸,生物精炼中的主要副产物之一,具备廉价易得、无毒、能量密度高以及可再生可降解等特性,将其应用于新能源利用与化学转化,不仅有助于甲酸应用领域的进一步拓展,还有助于解决面向未来的生物精炼技术中的一些共性瓶颈问题.本文简要回顾了甲酸利用的研究历史,总结了甲酸作为高效、多用途试剂与原料在化学品合成及生物质催化转化等方面的最新研究进展,并对利用甲酸活化来实现高效化学转化的基本原理及催化体系进行了对比分析,指出今后研究重点应着眼于努力提高甲酸的利用效率,同时实现高选择性合成两方面,并在此基础上进一步拓展其应用领域.在化学品合成方面,甲酸作为一种环境友好可再生的多功能试剂可应用于多种官能团的选择转化过程.作为一种高含氢量的氢转移试剂或还原剂,甲酸相较传统氢气具有操作简便可控、条件温和、具有良好化学选择性等优点,广泛应用于醛酮、硝基、亚胺、腈、炔烃、烯烃等的选择还原以制取相应的醇、胺、烯烃和烷烃类化合物,以及醇类和环氧化物的氢解和官能团去保护等过程.鉴于甲酸亦可用作C1原料,作为多用途的关键基础试剂甲酸还可应用于包括喹啉衍生物的还原甲酰化、胺类化合物甲酰化和甲基化,烯烃羰化以及炔烃还原水合等多级串联反应,是实现精细复杂有机分子高效简约绿色合成的重要途径.该类过程的挑战在于寻求对甲酸及特定官能团的可控活化兼具高选择性和高活性的多功能催化剂.此外,近期有研究表明以甲酸为C1原料还可通过催化歧化反应直接高选择性合成甲醇等大宗化学品.在生物质催化转化方面,甲酸的多功能特性为�Formic acid is available as a major byproduct from biorefinery processing and this together with its unique properties, including non-toxicity, favorable energy density, and biodegradability, make it an economically appealing and safe reagent for energy storage and chemical synthesis. This review provides an overview of novel recent achievements in green catalytic transformations that use biogenic formic acid as an efficient and versatile reagent. The examples selected demonstrate the advantages of formic acid in addressing the key issues（minimizing the use and generation of hazardous substances while maximizing productivity under mild and benign reaction conditions） in clean chemical transformation. Special emphasis is put on the prospects of formic acid for delivering new catalytic technology to produce a plethora of tailor-made products via the flexible and selective conversion of renewable biomass resources. The potential of formic acid as a renewable C1 feedstock for both bulk and fine chemical syntheses is also outlined with examples. The role of multifunctionality in catalyst design as a key aspect in developing new catalytic concepts capable of promoting new transformations to give unprecedented selectivity and efficiency is also discussed. This article is expected to advance research on sustainable, green and affordable bio-based processes as alternatives to traditional ones with the goal to develop a fully sustainable chemical industry based on renewable resources.

关 键 词：甲酸 新型催化 可再生氢能源 环境友好型试剂 化学合成 生物精炼 

分 类 号：O623.611[理学—有机化学]